Friction and normal interaction forces between irreversibly attached weakly charged polymer brushes

Polyelectrolyte brushes were built on mica by anchoring polystyrene-poly(acrylic acid) (PS-b-PAA) diblock copolymers at a controlled surface density in a polystyrene monolayer covalently attached to OH-activated mica surfaces. Compared to physisorbed polymer brushes, these irreversibly attached charged brushes allow the polymer grafting density to remain constant upon changes in environmental conditions (e.g., pH, salt concentration, compression, and shear). The normal interaction and friction forces as a function of surface separation distance and at different concentrations of added salt (NaCl) were investigated using a surface forces apparatus. The interaction force profiles were completely reversible both on loading and receding and were purely repulsive. For a constant polymer grafting density, the influence of the polyelectrolyte charges and the Debye screening effect on the overall interaction forces was investigated. The experimental interaction force profiles agree very well with scaling models developed for neutral and charged polymer brushes. The variation of the friction force between two PAA brushes in motion with respect to each other as a function of surface separation distance appeared to be similar to that observed with neutral brushes. This similarity suggests that the increase in friction is associated with an increase in mutual interpenetration upon compression as observed with neutral polymers. The effect of the PAA charges and added ions was more significant on the repulsive normal forces than on the friction forces. The reversible characteristics of the normal force profiles and friction measurements confirmed the strong attachment of the PAA brushes to the mica substrate. High friction coefficients (ca 0:3) were measured at relatively hi-fi pressures (40 atm) with no surface damage or polymer removal.